Supplementary material for thesis <i>"</i><i>Symmetry in copper and silver cryptates"</i>

The cryptand ligands imBT (1,4,7,10,13,16,21,24-Octaaza-bicyclo[8.8.8]hexacosa-4,6,13,15,21,23-hexaene) and amBT (1,4,7,10,13,16,21,24-Octaazabicycl0[8.8.8]hexacosane) form interesting disilver(I) and trisilver(I) cryptates, as well as a dicopper(I) and a well studied average valence dicopper(1.5) cryptate. Detailed structural and spectroscopic studies of the silver cryptates show that complex equilibria exist in solution, and the trisilver form appears to be thermodynamically favoured, the additional stabilisation apparently being due to argentophilic interactions.<br><br>An optically pure form of the dicopper(I) imBT cryptate was successfully obtained, and is undergoing X-ray diffraction studies aimed at determining whether a copper-copper interaction exists, by direct examination of the electron density.<br><br>Synthetic studies aimed at introducing substitution to the imBT and amBT ligands were complicated by competing reactions. A strategy to modify cryptand cavity size by incorporating asymmetric tetraamine caps succeeded, yielding dicopper(I) and disilver(I) cryptates with properties intermediate between cryptates incorporating the related symmetric caps.<br><br>Manganese(II) cryptates of imBT and amBT were investigated as potential MRl contrast agents, the iminocryptate showing surprisingly high relaxivity, despite the fact that no water molecules were located in the crystal structure.<br><br>The observation of high mass peaks in the FAB mass spectra of imBT and amBT cryptates suggests the presence of 6+4 Schiff base condensation products, as well as the more abundant 3+2 products. It has not proved possible to isolate these molecules as yet, however initial studies aimed at a rational synthesis of the 6+4 condensation products were made, as these ligands could be of great interest for modelling the recently reported CUz site.

穴状配体（cryptand ligand）imBT（1,4,7,10,13,16,21,24-八氮杂双环[8.8.8]二十六碳-4,6,13,15,21,23-六烯）与amBT（1,4,7,10,13,16,21,24-八氮杂双环[8.8.8]二十六烷）可形成有趣的二银(I)穴合物、三银(I)穴合物，以及二铜(I)穴合物与研究较为充分的平均价态二铜(1.5)穴合物。针对银基穴合物的详细结构与光谱学研究表明，其在溶液中存在复杂的配位平衡；其中三银(I)穴合物在热力学上更具优势，其额外的稳定性显然源于亲银相互作用（argentophilic interaction）。<br><br>研究人员成功获得了光学纯的二铜(I) imBT穴合物，目前正通过直接解析电子密度的X射线衍射（X-ray diffraction）实验，探究其分子内是否存在铜-铜相互作用。<br><br>针对imBT与amBT配体的取代修饰合成研究因竞争性副反应而进展受阻。研究人员通过引入不对称四胺帽调控穴状配体的空腔尺寸，成功得到了二铜(I)与二银(I)穴合物，其性能介于搭载相关对称帽结构的穴合物之间。<br><br>以imBT与amBT为配体的锰(II)穴合物被作为潜在磁共振成像（MRI）造影剂开展研究；尽管晶体结构中未发现配位水分子，该亚胺型穴合物却展现出出人意料的高弛豫率（relaxivity）。<br><br>在imBT与amBT穴合物的快原子轰击（FAB）质谱中观测到了高质量分子离子峰，这表明体系中存在6+4型希夫碱缩合（Schiff base condensation）产物与丰度更高的3+2型缩合产物。目前尚未成功分离得到这类分子，但研究人员已初步开展了6+4型缩合产物的可控合成研究——这类配体可用于模拟近期报道的CUz位点，具备重要研究价值。

搜集汇总

背景与挑战

背景概述

该数据集是论文《Symmetry in copper and silver cryptates》的补充材料，包含银(I)、铜(I)和锰(II)隐配体化合物的CIF结构文件，涉及imBT和amBT配体。数据集提供了这些化合物的结构、光谱分析和合成研究信息，重点探讨了银隐配体中的银-银相互作用和锰隐配体作为MRI造影剂的潜力。